Chitosan nanoparticles (chitosan NP) were effectively incorporated onto cotton fiber surfaces during a green adsorption without any cross-linking agents in this work. The interactions between cotton fibers and chitosan NP during the green adsorption were investigated by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), thermogravimetric-derivative thermogravimetry (TG-DTG) and scanning electron microscopy (SEM) in detail. The results indicated that the intermolecular hydrogen bond interactions exited between the hydroxyl groups of cotton fibers and the amino groups of chitosan NP, and progressively enhanced with the increase in chitosan NP mass concentrations. After chitosan NP adsorption, the acidity of fibers augmented and the crystallinity index of fibers declined owing to the increasing interactions. In addition, the hydrophobic interactions occurred between chitosan NP and crystalline cotton fibers, thereby resulting in the preferential adsorption onto the hydrophobic (2 0 0) crystallographic plane. © 2013 Elsevier Ltd.